CN107026256A - A kind of thermal cell positive electrode FexCo1‑xS2Powder and preparation method thereof - Google Patents
A kind of thermal cell positive electrode FexCo1‑xS2Powder and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention provides a kind of thermal cell positive electrode FexCo1‑ xS2Powder and preparation method thereof, the FexCo1‑xS20 ＜ x ＜ 1 in powder；The present invention is by combining two kinds of positive electrode CoS2And FeS2Advantage, prepare a kind of thermal cell positive electrode Fe using the method being combined of chemical precipitation and high temperature solid state reactionxCo1‑xS2Powder.The thermal cell positive electrode FexCo1‑xS2Powder both has FeS2The advantage of high power capacity and high voltage platform, has CoS again2Low-resistivity and the high advantage of heat endurance, are a kind of Novel hot cell positive materials.
Description
Technical field
Thermal cell positive electrode preparation field of the present invention, is related to a kind of thermal cell positive electrode FexCo1-xS2Powder and its system
Preparation Method.
Background technology
Thermal cell is also known as molten salt battery, and electrolyte is nonconducting solid at normal temperatures, and long term storage and heat activation are
Its two big feature, it is all significant in dual-use field.In civil area, fire alarm electricity, bad environments and temperature can be used as
The higher underground heat of degree and the various measuring instruments in oil and gas well drilling exploration process need to use power supply etc..
Now act as thermal cell positive electrode both at home and abroad has sulfide, chloride and oxide.With chlorination in chloride
Nickel is main representative, but because its preparation technology is immature, there is safety problem when using and extensively should without obtaining.In oxide
Main representative be LVO, it is the vanadium oxide that lithiumation is crossed, but its service life is shorter, electric discharge exist initial stage due to voltage spikes and
Electric discharge step problem.Sulfide is the optimal representative of thermal cell positive electrode, wherein should with ferrous disulfide and cobalt disulfide
With more maturation.
The A of CN 102339979 disclose a kind of method for preparing thin-film positive electrode for thermal batteries, and it can be prepared such as FeS2Deng positive pole material
Material；CN 102544482A disclose a kind of thermal cell CoS2The formula and its handling process of positive electrode.But due to FeS2Put
Electric energy power is low, is mismatched very much with lithium alloy negative pole, and monomer floating voltage only has 2.0V or so, is unfavorable for further improving battery
Specific energy；And it is used as positive active material FeS2Decomposition temperature be about 540 DEG C, (500 DEG C of left sides under the operating temperature of thermal cell
It is right), it is easy to occur pyrolysis, cause electric capacity to decline, it is impossible to discharge for a long time.CoS2Although electrical conductivity is high and thermally-stabilised
Property it is good, but capacity is low and is only capable of obtaining by artificial synthesized method, and price, stability are poor.
Therefore, the problem of thermal cell positive pole that a kind of excellent combination property how is made is urgent need to resolve.
The content of the invention
For problems of the prior art, the invention provides a kind of thermal cell positive electrode FexCo1-xS2Powder and
Its preparation method.The present invention is by combining two kinds of positive electrode CoS2And FeS2Advantage, it is anti-using chemical precipitation and high temperature solid-state
The method being combined answered prepares a kind of thermal cell positive electrode FexCo1-xS2Powder.The thermal cell positive electrode FexCo1- xS2Powder both has FeS2The advantage of high power capacity and high voltage platform, has CoS again2Low-resistivity and high excellent of heat endurance
Gesture, is a kind of Novel hot cell positive material.
For up to this purpose, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of thermal cell positive electrode FexCo1-xS2Powder, the FexCo1-xS2Powder
In 0 ＜ x ＜ 1, wherein x can be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 or 0.9 etc., it is not limited to cited
Numerical value, other numerical value are feasible in listed scope.
In the present invention, thermal cell positive electrode FexCo1-xS2Powder is to synthesize presoma Fe by chemical precipitationxCo1-xS,
Again by high temperature solid state reaction with presoma FexCo1-xS is made.
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, pass through
Following technical scheme, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
It is used as currently preferred technical scheme, the FexCo1-xS2The electrical conductivity of powder is 0.01~0.1 Ω m, example
Such as 0.01 Ω m, 0.02 Ω m, 0.03 Ω m, 0.04 Ω m, 0.05 Ω m, 0.06 Ω m, 0.07 Ω m, 0.08
Ω m, 0.09 Ω m or 0.1 Ω m etc., it is not limited to other numerical value in cited numerical value, listed scope
OK, discharge voltage is 1.5~2V, such as 1.5V, 1.6V, 1.7V, 1.8V, 1.9V or 2V, it is not limited to cited
Other numerical value are feasible in numerical value, listed scope.
Second aspect, the invention provides a kind of thermal cell positive electrode FexCo1-xS2Raw powder's production technology, the side
Method comprises the following steps：
(1) raw material source of iron and cobalt source are mixed in proportion and mixed solution is made；
(2) precipitating reagent is added in mixed solution made from step (1) and is sufficiently stirred for carrying out precipitation reaction, reaction gained
Sediment is obtained after precipitating scrubbed and filtration treatment；
(3) the vacuum dried processing of gained sediment obtains well mixed Fe in step (2)xCo1-xS dries powder；
(4) by the Fe in step (3)xCo1-xS dries powder and mixed with excessive S powder, under protective atmosphere, carries out chemical combination
The Fe containing S is made in reactionxCo1-xS2Powder；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder carries out removing sulphuring treatment under protective atmosphere, final to be made
FexCo1-xS2Powder.
In the present invention, the chemical formula of precipitation reaction is in step (2)：
xFeSO4·7H2O+(1-x)CoSO4·7H2O+Na2S·9H2O→FexCo1-xS↓+Na2SO4
The chemical formula of combination reaction is in step (4)：
FexCo1-xS+S=FexCo1-xS2
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, pass through
Following technical scheme, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the consumption of raw material source of iron and cobalt source makes to be made described in step (1)
Fe in mixed solution2+With Co2+Mol ratio be x:(1-x), wherein, 0 ＜ x ＜ 1, x can for 0.1,0.2,0.3,0.4,0.5,
0.6th, 0.7,0.8 or 0.9 etc., it is not limited to other numerical value are feasible in cited numerical value, listed scope.
In the present invention, the quality proportioning of the source of iron and Guyuan is because of obtained FexCo1-xS2X values in powder it is different without
Together.
Preferably, source of iron described in step (1) is ferrous sulfate and/or frerrous chloride.
Preferably, cobalt source described in step (1) is cobaltous sulfate and/or cobalt chloride.
Preferably, mixed solution is made described in step (1) is：By raw material in being dissolved in shape in distilled water at 20~30 DEG C
Into mixed solution.Herein, the solution temperature is normal temperature, is not limited in 20~30 DEG C.
As currently preferred technical scheme, precipitating reagent described in step (2) is water miscible sulfide.
Preferably, the precipitating reagent is Na2S·9H2O。
Preferably, the consumption of precipitating reagent described in step (2) is 20~50wt% more than its theoretical amount, for example
20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt% etc., it is not limited to cited numerical value,
Other numerical value are feasible in listed scope.
Preferably, mixing time described in step (2) is 5~10h, such as 5h, 6h, 7h, 8h, 9h or 10h, but not
It is only limitted to other numerical value in cited numerical value, listed scope feasible, more preferably 8h.
Preferably, stir speed (S.S.) described in step (2) is 100~150rad/min, such as 100rad/min, 110rad/
Min, 120rad/min, 130rad/min, 140rad/min or 150rad/min etc., it is not limited to cited numerical value,
Other numerical value are feasible in listed scope, more preferably 120rad/min.In the present invention, the stir speed (S.S.) need to be controlled
In certain limit, so that powder uniform and with large specific surface area is made.
Gained precipitation is carried out as currently preferred technical scheme, in step (2) repeatedly to wash and filter, extremely filtered
It is added dropwise after the aqueous solution containing barium ions and is produced without white precipitate in the filtrate of generation.
As currently preferred technical scheme, vacuum drying temperature described in step (3) is 100~150 DEG C, for example
100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc., it is not limited to cited numerical value, in listed scope its
His numerical value is feasible, more preferably 120 DEG C.
Preferably, the vacuum drying time described in step (3) be 12~24h, such as 12h, 14h, 16h, 18h, 20h,
22h or 24h etc., it is not limited to other numerical value are feasible in cited numerical value, listed scope, more preferably 16h.
Preferably, vacuum drying pressure is described in step (3)<10-3Pa。
As currently preferred technical scheme, protective gas described in step (4) is helium, argon gas, neon or nitrogen
In any one or at least two combination, combination typical case but non-limiting examples have：The combination of helium and argon gas, neon
With the combination of nitrogen, the combination of helium, argon gas and neon, helium, argon gas, the combination of neon and nitrogen etc., more preferably
Argon gas.
Preferably, the temperature of combination reaction described in step (4) be 600~700 DEG C, such as 600 DEG C, 610 DEG C, 620 DEG C,
630 DEG C, 640 DEG C, 650 DEG C, 660 DEG C, 670 DEG C, 680 DEG C, 690 DEG C or 700 DEG C etc., it is not limited to cited numerical value,
Other numerical value are feasible in listed scope, more preferably 650 DEG C.In the present invention, if the temperature of combination reaction is too high, it can make
Synthetic product is decomposed；Reactant reaction can be made incomplete if the temperature of combination reaction is too low.
Preferably, the time of combination reaction described in step (4) is 4~6h, such as 4h, 4.5h, 5h, 5.5h or 6h,
It is not limited to other numerical value are feasible in cited numerical value, listed scope, more preferably 5h.
Preferably, the heating rate of combination reaction described in step (4) is 3~10 DEG C/min, such as 3 DEG C/min, 4 DEG C/
Min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min etc., it is not limited to cited
Other numerical value are feasible in numerical value, listed scope, more preferably 5 DEG C/min.
As currently preferred technical scheme, protective gas described in step (5) is helium, argon gas, neon or nitrogen
In any one or at least two combination, combination typical case but non-limiting examples have：The combination of helium and argon gas, neon
With the combination of nitrogen, the combination of helium, argon gas and neon, helium, argon gas, the combination of neon and nitrogen etc., more preferably
Argon gas.
Preferably, sulphur removal is processed as described in step (5)：By the Fe containing S under protective atmospherexCo1-xS2Powder in 500~
At 600 DEG C be incubated 2~4h, wherein sulphur removal temperature can for 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C,
570 DEG C, 580 DEG C, 590 DEG C or 600 DEG C etc., it is not limited to other numerical value are feasible in cited numerical value, listed scope；
Soaking time can be 2h, 3h or 4h etc., it is not limited to other numerical value are feasible in cited numerical value, listed scope.
Preferably, it is 3~10 DEG C/min, such as 3 DEG C/min, 4 that the heating rate in sulphuring treatment is removed described in step (5)
DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min etc., it is not limited to cited
Numerical value, other numerical value are feasible in listed scope, more preferably 5 DEG C/min.
As currently preferred technical scheme, it the described method comprises the following steps：
(1) mix molten after mixing raw material source of iron and source of iron in proportion and in being dissolved in distilled water to be formed at 20~30 DEG C
Liquid；
(2) it is slowly added to precipitating reagent Na in mixed solution made from step (1)2S·9H2O and with 120rad/min speed
Rate is sufficiently stirred for 8h and carries out precipitation reaction, and reaction gained precipitation is through repeatedly washing and filters, and is added dropwise in the filtrate produced to filtering
Produced after the aqueous solution containing barium ions without white precipitate, obtain sediment；
(3) gained sediment obtains well mixed Fe in vacuum dried processing 16h at 120 DEG C in step (2)xCo1- xS dries powder；
(4) by the Fe in step (3)xCo1-xS dries powder and mixed with excessive S powder, under an argon atmosphere, in 650 DEG C
The Fe containing S is made in lower progress combination reaction 5hxCo1-xS2Powder；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder under an argon atmosphere at 500~600 DEG C insulation 2~
4h carries out removing sulphuring treatment, and Fe is finally madexCo1-xS2Powder.
Compared with prior art, the invention has the advantages that：
The present invention synthesizes Fe by chemical precipitation firstxCo1-xS2The presoma Fe of powderxCo1-xS, vacuum drying, then lead to
Cross high temperature solid state reaction kinetics FexCo1-xS2Powder.Fe made from methods describedxCo1-xS2The specific surface area of powder is big；Made with it
For thermode positive electrode, current density when being significantly reduced electric discharge advantageously reduces activation polarization.
Fe of the present inventionxCo1-xS2Powder combines CoS2And FeS2Advantage, i.e., with FeS2High power capacity and high voltage
The advantage of platform；There is CoS again2Low-resistivity and the high advantage of heat endurance, be a kind of Novel hot cell positive material, be
The performance of Novel hot cell positive material, which is improved, provides new approaches and new technology.
Meanwhile, technique of the present invention is simple, FexCo1-xS2The resistivity of powder is low, about 0.01~0.1 Ω m, puts
Piezoelectric voltage is high, about 2V or so, is conducive to obtaining high-power high-capacity thermal cell.
Brief description of the drawings
Fig. 1 is thermal cell positive electrode Fe of the present inventionxCo1-xS2The process chart of raw powder's production technology；
Fig. 2 is Fe made from the embodiment of the present invention 10.5Co0.5S2The XRD of powder；
Fig. 3 is Fe made from the embodiment of the present invention 10.5Co0.5S2The SEM figures of powder.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides thermal cell positive electrode FexCo1-xS2Powder and preparation method thereof, it is described
Method is as shown in figure 1, comprise the following steps：
(1) raw material source of iron and cobalt source are mixed in proportion and mixed solution is made；
(2) precipitating reagent is added in mixed solution made from step (1) and is sufficiently stirred for carrying out precipitation reaction, reaction gained
Sediment is obtained after precipitating scrubbed and filtration treatment；
(3) the vacuum dried processing of gained sediment obtains well mixed Fe in step (2)xCo1-xS dries powder；
(4) by the Fe in step (3)xCo1-xS dries powder and mixed with excessive S powder, under protective atmosphere, carries out chemical combination
The Fe containing S is made in reactionxCo1-xS2Powder；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder carries out removing sulphuring treatment under protective atmosphere, final to be made
FexCo1-xS2Powder.
It is below present invention typical case but non-limiting example：
Embodiment 1：
Present embodiments provide Fe0.5Co0.5S2Raw powder's production technology, the described method comprises the following steps：
(1) 139g FeSO are weighed4·7H2O and 140.5g CoSO4·7H2O is as initial feed, by the two simultaneously in room
In being dissolved under temperature and stir be completely dissolved it；
(2) to being slowly added to 288g precipitating reagents Na in mixed solution made from step (1)2S·9H2O, during which with
130rad/min speed is sufficiently stirred for 6h, obtains black precipitate Fe0.5Co0.5S, and sediment is washed and filtered,
It is added dropwise in the filtrate produced to filtering and contains Ba2+The aqueous solution after without white precipitate produce, obtain sediment；
(3) gained sediment obtains well mixed in vacuum dried processing 21h at 120 DEG C in step (2)
Fe0.5Co0.5S dries powder；
(4) by the Fe in step (3)0.5Co0.5S drying powders are mixed with 64g distillation S powder and are placed in tube-type atmosphere furnace,
Under argon gas atmosphere, the Fe containing S is made in carrying out combination reaction 4h at 650 DEG C0.5Co0.5S2Powder, wherein heating rate be 5 DEG C/
min；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder is removed in insulation 2h at 550 DEG C under an argon atmosphere
Sulphuring treatment, wherein heating rate are 5 DEG C/min, and Fe is finally made0.5Co0.5S2Powder.
Gained Fe0.5Co0.5S2X-ray diffraction (XRD) figure of powder as shown in Fig. 2 SEM (SEM) figure such as
Shown in Fig. 3.From Fig. 2 it can be seen that products therefrom thing is mutually single in Fig. 3, particle size is 200~500nm.
Gained Fe0.5Co0.5S2The resistivity of powder is 0.04 Ω m, and discharge voltage is 1.92V, with excellent performance.
Embodiment 2：
Present embodiments provide Fe0.7Co0.3S2Raw powder's production technology, the described method comprises the following steps：
(1) 194.6g FeSO are weighed4·7H2O and 84.3g CoSO4·7H2O as initial feed, will the two simultaneously in
In being dissolved at room temperature and stir be completely dissolved it；
(2) to being slowly added to 288g precipitating reagents Na in mixed solution made from step (1)2S·9H2O, during which with
100rad/min speed is sufficiently stirred for 10h, obtains black precipitate Fe0.7Co0.3S, and sediment is washed and filtered,
It is added dropwise in the filtrate produced to filtering and contains Ba2+The aqueous solution after without white precipitate produce, obtain sediment；
(3) gained sediment obtains well mixed in vacuum dried processing 20h at 120 DEG C in step (2)
Fe0.7Co0.3S dries powder；
(4) by the Fe in step (3)0.7Co0.3S drying powders are mixed with 64g distillation S powder and are placed in tube-type atmosphere furnace,
Under argon gas atmosphere, the Fe containing S is made in carrying out combination reaction 4h at 650 DEG C0.7Co0.3S2Powder, wherein heating rate be 3 DEG C/
min；
(5) by the Fe containing S made from step (4)0.7Co0.3S2Powder is carried out in insulation 2h at 550 DEG C under an argon atmosphere
Except sulphuring treatment, wherein heating rate is 3 DEG C/min, and Fe is finally made0.7Co0.3S2Powder.
Gained Fe0.7Co0.3S2The resistivity of powder is 0.08 Ω m, and discharge voltage is 1.98V, with excellent performance.
Embodiment 3：
Present embodiments provide Fe0.5Co0.5S2Raw powder's production technology, methods described is except stir speed (S.S.) in step (2)
For 150rad/min, mixing time is 5h；Vacuum drying temperature is 100 DEG C, drying time extra 24h in step (3)；Step
(4) combination reaction temperature is 700 DEG C in, and the reaction time is 5h, and heating rate is 10 DEG C/min；Sulphur removal temperature is in step (5)
600 DEG C, the sulphur removal time is 3h, and heating rate is outside 10 DEG C/min, unclassified stores consumption and preparation process with phase in embodiment 1
Together, Fe is finally made0.5Co0.5S2Powder.
Gained Fe0.5Co0.5S2The resistivity of powder is 0.04 Ω m, and discharge voltage is 1.92V, with excellent performance.
Embodiment 4：
Present embodiments provide Fe0.7Co0.3S2Raw powder's production technology, methods described in step (3) except being dried in vacuo
Temperature is 150 DEG C, drying time extra 12h；Combination reaction temperature is 600 DEG C in step (4), and the reaction time is 6h；Step (5)
Middle sulphur removal temperature is 500 DEG C, and the sulphur removal time is that unclassified stores consumption is in the same manner as in Example 2 with preparation process, finally outside 4h
Fe is made0.7Co0.3S2Powder.
Gained Fe0.7Co0.3S2The resistivity of powder is 0.08 Ω m, and discharge voltage is 1.98V, with excellent performance.
Integrated embodiment 1-4 can be seen that the present invention and synthesize Fe by chemical precipitation firstxCo1-xS2The presoma of powder
FexCo1-xS, vacuum drying, then Fe is synthesized by high temperature solid state reactionxCo1-xS2Powder.Fe made from methods describedxCo1-xS2Powder
The specific surface area of body is big；Using it as thermal cell positive electrode, current density when being significantly reduced electric discharge advantageously reduces electrification
Learn polarization.
Fe of the present inventionxCo1-xS2Powder combines CoS2And FeS2Advantage, i.e., with FeS2High power capacity and high voltage
The advantage of platform；There is CoS again2Low-resistivity and the high advantage of heat endurance, be a kind of Novel hot cell positive material, be
The performance of Novel hot cell positive material, which is improved, provides new approaches and new technology.
Meanwhile, technique of the present invention is simple, FexCo1-xS2The resistivity of powder is low, can be 0.01~0.1 Ω m, put
Piezoelectric voltage is high, about 2V or so, is conducive to obtaining high-power high-capacity thermal cell.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of thermal cell positive electrode FexCo1-xS2Powder, it is characterised in that the FexCo1-xS20 ＜ x ＜ 1 in powder.
2. thermal cell positive electrode Fe according to claim 1xCo1-xS2Powder, it is characterised in that the FexCo1-xS2Powder
The Ω m of resistivity 0.01~0.1 of body, discharge voltage is 1.5~2V.
3. a kind of thermal cell positive electrode FexCo1-xS2Raw powder's production technology, it is characterised in that methods described includes following step
Suddenly：
(1) raw material source of iron and cobalt source are mixed in proportion and mixed solution is made；
(2) precipitating reagent is added in mixed solution made from step (1) and is sufficiently stirred for carrying out precipitation reaction, reaction gained is precipitated
Sediment is obtained after scrubbed and filtration treatment；
(3) the vacuum dried processing of gained sediment obtains well mixed Fe in step (2)xCo1-xS dries powder；
(4) by the Fe in step (3)xCo1-xS dries powder and mixed with excessive S powder, under protective atmosphere, carries out combination reaction
The Fe containing S is madexCo1-xS2Powder；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder carries out removing sulphuring treatment under protective atmosphere, final to be made
FexCo1-xS2Powder.
4. preparation method according to claim 3, it is characterised in that the use of raw material source of iron and cobalt source described in step (1)
Measure to make Fe in the mixed solution being made2+With Co2+Mol ratio be x:(1-x), wherein, 0 ＜ x ＜ 1；
Preferably, source of iron described in step (1) is ferrous sulfate and/or frerrous chloride；
Preferably, cobalt source described in step (1) is cobaltous sulfate and/or cobalt chloride etc.；
Preferably, mixed solution is made described in step (1) is：Raw material is mixed in being dissolved in formation in distilled water at 20~30 DEG C
Close solution.
5. the preparation method according to claim 3 or 4, it is characterised in that precipitating reagent described in step (2) is water miscible
Sulfide；
Preferably, the precipitating reagent is Na2S·9H2O；
Preferably, the consumption of precipitating reagent described in step (2) is 20~50wt% more than its theoretical amount；
Preferably, mixing time described in step (2) is 5~10h, more preferably 8h；
Preferably, stir speed (S.S.) described in step (2) is 100~150rad/min, more preferably 120rad/min.
6. the preparation method according to claim any one of 3-5, it is characterised in that precipitate and carry out to gained in step (2)
It is added dropwise after the aqueous solution containing barium ions and is produced without white precipitate in repeatedly washing and filtering, the filtrate produced to filtering.
7. the preparation method according to claim any one of 3-6, it is characterised in that vacuum drying described in step (3)
Temperature is 100~150 DEG C, more preferably 120 DEG C；
Preferably, the vacuum drying time described in step (3) is 12~24h, more preferably 16h；
Preferably, vacuum drying pressure is described in step (3)<10-3Pa。
8. the preparation method according to claim any one of 3-7, it is characterised in that protective gas is described in step (4)
Any one in helium, argon gas, neon or nitrogen or at least two combination, more preferably argon gas；
Preferably, the temperature of combination reaction described in step (4) is 600~700 DEG C, more preferably 650 DEG C；
Preferably, the time of combination reaction described in step (4) is 4~6h, more preferably 5h；
Preferably, the heating rate of combination reaction described in step (4) is 3~10 DEG C/min, more preferably 5 DEG C/min.
9. the preparation method according to claim any one of 3-8, it is characterised in that protective gas is described in step (5)
Any one in helium, argon gas, neon or nitrogen or at least two combination, more preferably argon gas；
Preferably, sulphur removal is processed as described in step (5)：By the Fe containing S under protective atmospherexCo1-xS2Powder is in 500~600
2~4h is incubated at DEG C；
Preferably, the heating rate in sulphuring treatment is removed described in step (5) for 3~10 DEG C/min, more preferably 5 DEG C/
min。
10. the preparation method according to claim any one of 3-9, it is characterised in that the described method comprises the following steps：
(1) mixed solution is formed after mixing raw material source of iron and cobalt source in proportion and in being dissolved at 20~30 DEG C in distilled water；
(2) it is slowly added to precipitating reagent Na in mixed solution made from step (1)2S·9H2O is simultaneously filled with 120rad/min speed
Stirring 8h is divided to carry out precipitation reaction, reaction gained is precipitated through repeatedly washing and filtered, and baric is added dropwise in the filtrate that extremely filtering is produced
Produced after the aqueous solution of ion without white precipitate, obtain sediment；
(3) gained sediment obtains well mixed Fe in vacuum dried processing 16h at 120 DEG C in step (2)xCo1-xS is dried
Powder；
(4) by the Fe in step (3)xCo1-xS dries powder and mixed with excessive S powder, under an argon atmosphere, in progress at 650 DEG C
The Fe containing S is made in combination reaction 5hxCo1-xS2Powder；
(5) by the Fe containing S made from step (4)xCo1-xS2Powder enters in 2~4h of insulation at 500~600 DEG C under an argon atmosphere
Row removes sulphuring treatment, and Fe is finally madexCo1-xS2Powder.
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| CN108539195A (en) * | 2018-04-10 | 2018-09-14 | 上海空间电源研究所 | A kind of thermal cell solid solution FexCo1-xS2 positive electrodes and preparation method thereof |
| CN109052486A (en) * | 2018-07-02 | 2018-12-21 | 中南大学 | A kind of thermal cell single-phase positive electrode and preparation method thereof, application |
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| CN108110269A (en) * | 2017-12-13 | 2018-06-01 | 贵州梅岭电源有限公司 | One kind can work long hours thermal cell under high ambient conditions |
| CN108511750B (en) * | 2018-04-04 | 2020-11-24 | 武汉理工大学 | Multi-metal sulfide catalyst for lithium air battery and preparation method thereof |
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| CN109052486A (en) * | 2018-07-02 | 2018-12-21 | 中南大学 | A kind of thermal cell single-phase positive electrode and preparation method thereof, application |
| CN109052486B (en) * | 2018-07-02 | 2019-08-09 | 中南大学 | A kind of thermal cell single-phase positive electrode and preparation method thereof, application |
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| CN111129490A (en) * | 2019-12-06 | 2020-05-08 | 中国科学院过程工程研究所 | Single-phase NiS2Large-scale preparation method of powder |
| CN111129490B (en) * | 2019-12-06 | 2021-12-03 | 中国科学院过程工程研究所 | Single-phase NiS2Large-scale preparation method of powder |
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